Insecticidal azoles

ABSTRACT

The present invention relates to novel heterocyclic compounds of formula (I) 
                 
 
where A, R1, R2, Y, Z, and n are defined in the disclosure, to processes for their preparation, and to their use as crop protection agents, in particular for controlling animal pests.

The present patent application has been filed under 35 U.S.C. 371 as anational stage application of PCT/EP02/04176, filed Apr. 16, 2002, whichwas published in German as International Patent Publication WO02/085,915 on Oct. 31, 2003, which is entitled to the right of priorityof German Patent Application DE 101 19 422.6, filed Apr. 20, 2001.

The present invention relates to novel heterocyclic compounds, toprocesses for their preparation and to their use as crop protectionagents, in particular for controlling animal pests.

Various substituted iminobicyles, such as, for example,6-(2-methylaminoethyl-imino)-2,3,4,8-tetrahydro-6H-thiazolo[3,4-a]pyrimidinehydrochloride, are already known as pharmacologically active compoundshaving a blood pressure-lowering effect. However, a use as cropprotection agents and in particular for controlling animal pests hashitherto not been disclosed (cf. U.S. Pat. No. 3,578,666).

Other substituted iminobicycles, such as, for example,5-imino-2,3-dihydroimidazo[1,2-c]thiazoles are known (cf. U.S. Pat. No.3,555,039). Certain iminobicycles of this structural type, such as, forexample, 7-phenyl-5-imino-2,3-dihydro-1H,5H-imidazo[1,2-c]thiazolehydrochloride, have blood pressure-lowering and central nervoussystem-stimulating activity. However, nothing has been disclosedconcerning the use as crop protection agents, in particular forcontrolling animal pests.

This invention now provides novel heterocyclic compounds of the formula(I)

in which

-   A represents in each case optionally substituted aryl or hetaryl or    heterocyclyl,-   R¹ represents hydrogen or C₁-C₃-alkyl,-   R² represents hydrogen, C₁-C₃-alkyl or in each case optionally    substituted aryl or hetaryl,-   n represents 2, 3 or 4,-   Y represents N—CN or N—NO₂,-   Z represents S, SO, SO₂ or NR³ and-   R³ represents hydrogen or C₁-C₃-alkyl,

Furthermore, it has been found that the compounds of the formula (I) areobtained when compounds of the formula (II)

are reacted with suitable cyanating agents (to obtain compounds of theformula (I) in which Y represents N—CN) or with suitable nitratingagents (to obtain compounds of the formula (I) in which Y representsN—NO₂).

Finally, it has been found that the novel compounds of the formula (I)have strongly pronounced biological properties and are suitableespecially for controlling animal pests, in particular insects,arachnids and nematodes, encountered in agriculture, in forests, in theprotection of stored products and materials and in the hygiene sector.

The formula (I) provides a general definition of the compounds accordingto the invention.

Preferred substituents or ranges of the radicals listed in the formulaementioned above and below are illustrated below.

-   A preferably represents optionally halogen-, cyano-, nitro-,    C₄-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy- or    C₁-C₄-haloalkoxy-substituted phenyl.-   A preferably further represents pyrazolyl, 1,2,4-triazolyl,    oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl,    pyridyl, pyrazinyl or pyrimidinyl, which are optionally substituted    by fluorine, chlorine, bromine, cyano, nitro, C₁-C₂-alkyl (which is    optionally substituted by fluorine and/or chlorine), C₁-C₂-alkoxy    (which is optionally substituted by fluorine and/or chlorine),    C₁-C₂-alkylthio (which is optionally substituted by fluorine and/or    chlorine) or C₁-C₂-alkylsulphonyl (which is optionally substituted    by fluorine and/or chlorine).-   A furthermore preferably represents an optionally halogen- or    C₁-C₃-alkyl-substituted saturated C₅-C₆-cycloalkyl radical in which    one methylene group is replaced by O or S.-   R¹ preferably represents hydrogen, methyl, ethyl, n-propyl or    i-propyl.-   R² preferably represents hydrogen, methyl, ethyl, n-propyl,    i-propyl, represents optionally halogen-, cyano-, nitro-,    C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy- or    C₁-C₄-haloalkoxy-substituted phenyl or represents pyrazolyl,    1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,    1,2,5-thiadiazolyl, pyridyl, pyrazinyl or pyrimidinyl which are    optionally substituted by fluorine, chlorine, bromine, cyano, nitro,    C₁-C₂-alkyl (which is optionally substituted by fluorine and/or    chlorine), C₁-C₂-alkoxy (which is optionally substituted by fluorine    and/or chlorine), C₁-C₂-alkylthio (which is optionally substituted    by fluorine and/or chlorine) or C₁-C₂-alkylsulphonyl (which is    optionally substituted by fluorine and/or chlorine).-   n preferably represents 2, 3 or 4 (in particular 2 or 3).-   Y preferably represents N—CN or N—NO₂,-   Z preferably represents S or NR³.-   R³ preferably represents hydrogen, methyl, ethyl, n-propyl or    i-propyl.-   A particularly preferably represents thiazolyl or pyridyl, which are    each optionally substituted by halogen (in particular chlorine) or    C₁-C₃-alkyl (in particular methyl).-   A furthermore particularly preferably represents an optionally    halogen (in particular chlorine) or C₁-C₃-alkyl (in particular    methyl-) substituted tetrahydrofuryl radical.-   R¹ particularly preferably represents hydrogen or methyl.-   R² particularly preferably represents hydrogen, methyl, or    represents phenyl which is optionally substituted by halogen, cyano    or by in each case optionally fluorine- or chlorine-substituted    methyl, ethyl, methoxy or ethoxy, or represents thiazolyl, pyridyl    or pyrazinyl.-   n particularly preferably represents 2 or 3.-   Y particularly preferably represents NCN or NNO₂.-   Z particularly preferably represents S or NR³.-   R³ particularly preferably represents hydrogen or methyl.-   A very particularly preferably represents one of the radicals-   R¹ very particularly preferably represents hydrogen or methyl, in    particular hydrogen.-   R² very particularly preferably represents hydrogen or methyl.-   n very particularly preferably represents 2 or 3.-   Y very particularly preferably represents NCN-   Y furthermore very particularly preferably represents NNO₂.-   Z very particularly preferably represents S or NR³.-   R³ very particularly preferably represents hydrogen or methyl.

In a particular group of compounds of the formula (I), n represents 2.

In a further particular group of compounds of the formula (I); nrepresents 3.

In a further particular group of compounds of the formula (I), Yrepresents N—CN.

In a further particular group of compounds of the formula (I), Yrepresents N—NO₂.

In a further particular group of compounds of the formula (I), Arepresents

In a further particular group of compounds of formula (I), A represents

In a further particular group of compounds of the formula (I), Arepresents

The general or preferred radical definitions or illustrations listedabove apply to the end products and, correspondingly, to the startingmaterials and intermediates. The radical definitions can be combinedwith one another as desired, i.e. including combinations between therespective preferred ranges.

Preference according to the invention is given to the compounds of theformula (I) which contain a combination of the meanings listed above asbeing preferred.

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

In the radical definitions given above and below, hydrocarbon radicals,such as alkyl, are in each case straight-chain or branched as far asthis is possible—including in combination with heteroatoms, such as inalkoxy.

Using, for example, the starting materials cyanogen bromide andcompounds of the structure A below, the course of the process accordingto the invention can be represented by the reaction scheme below:

The compounds of the formula (II) are novel and also form part of thesubject-matter of the present invention.

Depending in particular on the meaning of the variable Z, variousmethods may be considered for preparing the compounds of the formula(II). Some compounds of the formula (I), too, can be prepared by othermethods.

This is illustrated initially by formula scheme I below.

The reactions described in Formula Scheme I can be carried out in agenerally known manner.

The compounds of the formula (V) can be converted by reaction withsulphurizing reagents into the compounds of the formula (IV).

In the literature, a large number of different sulphurizing agents, suchas, for example, hydrogen sulphide (H₂S), hydrogen sulphide/hydrogenchloride (H₂S/HCl), hydrogen persulphide/hydrogen chloride (H₂S₂/HCl),di(diethylaluminium) sulphide [(Et₂Al)₂S], polymeric ethylaluminiumsulphide [(EtAlS)_(n)], silicon disulphide (SiS₂), diboron trisulphide(B₂S₃), phosphorus pentachloride/dialuminium trisulphide/sodium sulphate(PCl₅/Al₂S₃/Na₂SO_(A)), sodium sulphide/sulphuric acid (Na₂S/H₂SO₄),diphosphorus pentasulphide (P₂S₅), diphosphorus pentasulphide/pyridine(P₂S₅/Py), diethylthiocarbamoyl chloride, diphosphoruspentasulphide/triethylamine (P₂S₅/NEt₃), diphosphoruspentasulphide/n-butyllithium (P₂S₅/n-BuLi), diphosphoruspentasulphide/sodium bicarbonate (P₂S₅/NaHCO₃; “Scheeren's Reagent”,formation of Na²⁺[P₄S₁₀O]²⁻), diphosphorus pentasulphide/methanol(P₂S₅/MeOH), SCN—CO—OEt, PSCl_(x)(NMe₂)_(3-X)(X=0-3),bis(tricyclohexyltin)sulphide/boron trihalide [(C₆H₁₁)₃Sn]S₂+BX₃ (X=Cl,F), EP 0 280 867 (1988), bis(1,5-cyclooctanediylboryl) sulphide[(9-BBN)₂S] as sulphurizing agent or as phosphorus pentasulphidesubstitute2,4-bis(methylthio)-1,3,2,4-dithiadiphosphetane-2,4-disulphide “DavyReagent Methyl” (DR-Me),2,4-bis(ethylthio)-1,3,2,4-dithiadiphosphetane-2,4-disulphide “DavyReagent Ethyl” (DR-Et), 2,4-bis(p-tolylthio)-1,3,2,4-dithiadiphosphetane2,4-disulphide “Davy Reagent p-Tolyl or Heimgartner Reagent” (DR-T),2,4-bis-(4-phenoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane“Belleau's Reagent (BR)”,2,4-bis-(4-phenylthiophenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane,2,4-bis(4-methoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane“Lawesson's Reagent (LR)” (cf. Davy Reagent: H. Heimgartner et al.,Helv. Chim Acta 70, 1987, P. 1001; Belleau's Reagent: Tetrahedron 40,1984, p. 2047; Tetrahedron 40, 1984, p. 2663; Tetrahedron Letters 24,1983, p. 3815; I. Thomson et al., Org. Synth. 62, 1984, p. 158 and theliterature cited therein; D. Brillon Synthetic Commun. 20 (19), 1990, P.3085 and the literature cited therein; selective thionation ofoligopeptides; K. Clausen et al., J. Chem. Soc., Perkin Trans I 1984,785; O. E. Jensen et al., Tetrahedron 41, 1985, p. 5595; Reviews on“Lawesson's Reagent, (LR)”: R. A. Cherkasov et al., Tetrahedron 41,1985, p. 2567; M. P. Cava et al., Tetrahedron 41, 1985, p. 5061; diborylsulphide: Liebigs Ann. Chem. 1992, p. 1081 and literature cited therein;Metzner et al. in Sulphur Reagents in Organic Synthesis, B. Harcourt:London 1994, Academic Press, p. 44-45) have been described in theliterature.

Alternative possibilities are also reaction sequences such as, forexample, O-alkylation with R₃O⁺BF₄O⁻(R: methyl, ethyl) (H. Meerwein etal., Justus Lebigs Ann. Chem. 641, (1961) p. 1) and subsequent reactionof the intermediates with anhydrous NaSH (R. E. Eibeck, Inorg. Syn. 7,(1963) p. 128), the in-situ formation of chloroiminium salts andsubsequent reaction with tetrathiomolybdates, in particularbenzyltriethylammonium tetrathiomolybdate [(Ph-CH₂—NEt₃)₂MoS₄](Tetrahedron Lett. 36 (45), 1995, p. 8311) or hexamethyldisilathiane(TMS₂S). (TMS: trimethylsilyl; P. L. Fuchs et al., J. Org. Chem. 59,1994, p. 348).

Preferred sulphurizing agents are phosphorus reagents, such as, forexample, diphosphorus pentasulphide (P₂S₅), diphosphoruspentasulphide/pyridine (P₂S₅/Py), diphosphoruspentasulphide/triethylamine (P₂S₅/NEt₃), diphosphoruspentasulphide/sodium bicarbonate (P₂S₅/NaHCO₃ “Scheeren's Reagent”) or,particularly preferably, the racemisation-free2,4-bis(4-methoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane (LR:Lawesson's Reagent) (K. Clausen, M. Thorsen, S. O. Lawesson Tetrahedron37, 1981, p. 3635),2,4-bis-(4-phenoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane“Belleau's Reagent (BR)” or2,4-bis-(4-phenylthiophenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane.

In general, it is advantageous to carry out this process in the presenceof diluents. Diluents are advantageously employed in such an amount thatduring the entire process the reaction mixture remains readilystirrable. Suitable diluents for carrying out the process according tothe invention are all inert organic solvents.

Examples which may be mentioned are: halogenated hydrocarbons, inparticular chlorinated hydrocarbons, such as tetrachloroethylene,tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane,chloroform, carbon tetrachloride, trichloroethane, trichloroethylene,pentachloroethane, difluorobenzene, 1,2-dichloroethane, chlorobenzene,bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene;alcohols, such as methanol, ethanol, isopropanol, butanol; ethers, suchas ethyl propyl ether, methyl tert-butyl ether, anisole, phenetol,cyclohexyl methyl ether, dimethyl ether, diethyl ether, dipropyl ether,diisopropyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether,ethylene glycol dimethyl ether, tetrahydrofuran, dioxane,dichlorodiethyl ether and ethylene oxide and/or propylene oxidepolyethers; amines, such as trimethylamine, triethylamine,tripropylamine, tributylamine, N-methyl-morpholine, pyridine andtetramethylenediamine; nitrated hydrocarbons such as nitromethane,nitroethane, nitropropane, nitrobenzene, chloronitrobenzene,o-nitrotoluene; nitriles, such as acetonitrile, propionitrile,butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile andalso compounds such as tetrahydrothiophene dioxide and dimethylsulphoxide, tetramethylene sulphoxide, dipropyl sulphoxide, benzylmethyl sulphoxide, diisobutyl sulphoxide, dibutyl sulphoxide, diisoamylsulphoxide; sulphones, such as dimethyl sulphone, diethyl sulphone,dipropyl sulphone, dibutyl sulphone, diphenyl sulphone, dihexylsulphone, methyl ethyl sulphone, ethyl propyl sulphone, ethyl isobutylsulphone and pentamethylene sulphone; aliphatic, cycloaliphatic oraromatic hydrocarbons, such as pentane, hexane, heptane, octane, nonaneand industrial hydrocarbons, for example White Spirits having componentsof boiling points in the range of, for example, from 40° C. to 250° C.,cymene, petroleum fractions within a boiling point range of from 70° C.to 190° C., cyclohexane, methylcyclohexane, petroleum ether, ligroin,octane, benzene, toluene, chlorobenzene, bromobenzene, nitrobenzene,xylene; esters, such as methyl acetate, ethyl acetate, butyl acetate,isobutyl acetate, and also dimethyl carbonate, dibutyl carbonate,ethylene carbonate; amides, such as hexamethylphosphoric triamide,formamide, N-methylformamide, N,N-dimethylformamide,N,N-dipropylformamide, N,N-dibutylformamide, N-methylpyrrolidine,N-methylcaprolactam, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidine,octylpyrrolidone, octylcaprolactam, 1,3-dimethyl-2-imidazolinedione,N-formylpiperidine, N,N′-1,4-diformylpiperazine; ketones, such asacetone, acetophenone, methyl ethyl ketone, methyl butyl ketone.

Process according to the invention can, of course, also be carried outin mixtures of the solvents and the diluents mentioned.

The diluents to be used depend on the sulphurizing agent used in eachparticular case.

However, preferred diluents for the thionation are aromatichydrocarbons, such as benzene, toluene, chlorobenzene, bromobenzene,nitrobenzene, or xylene, ethers, such as ethyl propyl ether, methyltert-butyl ether, anisole, phenetol, cyclohexyl methyl ether,tetrahydrofuran or dioxane.

By reaction with HgCl₂/(C₂H₅)₃N/H₂NCN the compounds of the formula (IV)can be converted directly into compounds of the formula (I) in which Yrepresents CN (cf. Can. J. Chem. 1985, 63, 3089 and also J. Med. Chem.1988, 31, 264).

The compounds of the formula (IV) can furthermore be converted byaminolysis with ammonia in the presence of mercury salts, by heatingwith ethanolic ammonia solution or by reaction with aqueous ammonia inthe presence of suitable oxidizing agents, such as, for example,tert-butyl hydroperoxide (TBHP), into compounds of the formula (II) (cf.M. G. Bock et al., J. Med. Chem. 1988, 31, 264-268; N. W. Jacobsen etal., Aust. J. Chem. 1987, 40, 491-499; T. Lindel et al., TetrahedronLett. 1997.38, (52), 8935-8938).

Reaction of the compounds of the formula (IV) (Z=NH) with alkyl iodidesin the presence of bases gives compounds of the formula (III) (see thefollowing references: T. Lindel et al., Tetrahedron Lett. 1997.38, (52),8935-8938 M. G. Bock et al., J. Med. Chem. 1988, 31, 264-268). In thecompounds of the formula (III), R represents, for example, alkyl,preferably methyl or ethyl. Compounds of the formula (III) in turn canbe converted in a manner which is known in principle by reaction with amixture of ammonia/ammonium chloride into compounds of the formula (II)(cf. T. Lindel et al., Tetrahedron Lett. 1997.38, (52), 8935-8938).

The compounds of the formula (II) can be converted with cyanating agentsor nitrating agents into compounds of the formula (I).

A suitable cyanating agent is, for example, cyanogen bromide (BrCN). Thereaction is carried out in a generally known manner (cf. also U.S. Pat.No. 4,098,791 and DE 29 16 140).

Nitrations can be carried out by customary processes as described, forexample, in Houben-Weyl, Methoden der Organischen Chemie, [Methods ofOrganic Chemistry], Volume XI/2 (Georg Thieme Verlag-Stuttgart 1958),pp. 99-116. Nitrating agents which may be mentioned are fumed or 100%strength nitric acid (preparation of anhydrous nitric acid cf. F. D.Chattaway, Soc. 97, 2100(1910), if appropriate in the presence ofsulphuric acid (W. J. Middleton et al., J. Heterocycl. Chem. 7,1045-1049 (1970); L. W. Deady et al., Aust. J. Chem. 35 (10), 2025-2034(1982); EP 0 192 060) or the use of nitric acid esters, acetyl nitrateor nitronium tetrafluoroborate. The reaction is preferably carried outin a generally known manner using acyl nitrate.

Compounds of the formula (V)

in which

-   A, Z, n, R¹ and R² are as defined above,    are obtained, for example, by reacting compounds of the formula (VI)    in which-   A and R¹ are as defined above and-   E represents a leaving group, such as, for example, Cl,    with compounds of the formula (VII)    in which-   R², n and Z are as defined above,    in the presence of a diluent, such as, for example,    N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or    acetonitrile and in the presence of acid acceptors, at temperatures    between 0° C. and 200° C., preferably at temperatures between 20° C.    and 150° C.

Suitable acid acceptors for the process according to the invention areall acid binders which are customarily used for such reactions.

Preference is given to using alkali metal and alkaline earth metalhydrides, such as lithium hydride, sodium hydride, potassium hydride andcalcium hydride, alkali metal and alkaline earth metal hydroxides, suchas lithium hydroxide, sodium hydroxide, potassium hydroxide and calciumhydroxide, alkali metal and alkaline earth metal carbonates andbicarbonates, such as sodium carbonate and potassium carbonate or sodiumbicarbonate and potassium bicarbonate and also calcium carbonate, alkalimetal acetates, such as sodium acetate and potassium acetate, alkalimetal alkoxides, such as sodium methoxide, ethoxide, propoxide,isopropoxide, butoxide, isobutoxide and tert-butoxide and potassiummethoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide andtert-butoxide, furthermore basic nitrogen compounds, such astrimethylamine, triethylamine, tripropylamine, tributylamine,diisobutylamine, dicyclohexylamine, ethyldiisopropylamine,ethyldicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine,N,N-dimethylbenzylamine, N,N-dimethylaniline, pyridine, 2-methyl-,3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl-and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN),1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and1,4-diazabicyclo[2.2.2]octane (DABCO).

The compounds of the formula (VI) where Z=S can be prepared, forexample, from compounds of the formula (VIII) (cf. R. C. F. Jones, J. R.Nichols, Tetrahedron Lett. 31(12), 1771-1774, 1990) by the followingroute (cf. U.S. Pat. No. 3,555,039).

where

-   R² is as defined above and-   M represents a monovalent cation, such as, for example, Na or K.

Compounds of the formula (IIIa)

in which

-   A, R¹ and R² are as defined above and-   R′ represents alkyl, preferably methyl or ethyl,    are obtained, for example, by reacting compounds of the formula    (IVa)    in which-   A, R¹ and R² are as defined above,    initially with an alkyl halide, preferably an alkyl iodide, in    particular methyl iodide or ethyl iodide, in the presence of a    diluent, such as acetone, and then liberating the end product of the    formula (IIIa) using a base, such as sodium carbonate, in the    presence of a diluent, such as acetone.

It is also possible to convert the compounds of the formula (III)directly into those compounds of the formula (I) in which Y representsCN. Suitable methods are described, for example, in JP 7126483 and Arch.Pharm., 303 (8), 625-633 (1970), the contents of which are expresslyincorporated in this application by way of reference.

Compounds of the formula (I) can also be prepared according to thereaction scheme below (cf. the Preparation Examples):

The compounds of the formula (I) in which Z represents SO or SO₂ can beprepared from compounds of the formula (I) in which Z represents S byoxidation according to customary processes, for example using suitableoxidising agents, such as peroxides, for example, hydrogen peroxide,tert-butyl peroxide, organic and inorganic peroxides or salts thereof,such as 3-chloroperbenzoic acid, peracetic acid, performic acid,dibenzoyl peroxide, permanganate, or using a mixture of potassiumperoxomonosulphate, 2 KHSO₅, KHSO₄ and a solvent or solvent mixture (forexample water, acetic acid, methanol, methylene chloride). The peroxidecan also be prepared in situ from another peroxide, for exampleperacetic acid from acetic acid and hydrogen peroxide (cf. also A. R.Katritzky, C. W. Rees in Comprehensive Heterocyclic Chemistry, PergamonPress, Oxford, N.Y., 1984, Vol. 3, p. 96; O. J. Brown et al. Chem. Soc.(C), 1971, p. 256).

The oxidation can also be initiated or accelerated by suitablecatalysts.

The active compounds having good plant tolerance and favourablewarm-blood toxicity are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene sector. They may be preferably used ascrop protection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

-   From the order of the Isopoda, for example, Oniscus asellus,    Armadillidium vulgare and Porcellio scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus.-   From the order of the Chilopoda, for example, Geophilus carpophagus    and Scutigera spp.-   From the order of the Symphyla, for example, Scutigerella    immaculata.-   From the order of the Thysanura, for example, Lepisma saccharina.-   From the order of the Collembola, for example, Onychiurus armatus.-   From the order of the Orthoptera, for example, Acheta domesticus,    Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp.    and Schistocerca gregaria.-   From the order of the Blattaria, for example, Blatta orientalis,    Periplaneta americana, Leucophaea maderae and Blattella germanica.-   From the order of the Dermaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Reticulitermes spp.-   From the order of the Phthiraptera, for example, Pediculus humanus    corporis, Haematopinus spp., Linognathus spp., Trichodectes spp. and    Damalinia spp.-   From the order of the Thysanoptera, for example, Hercinothrips    femoralis, Thrips tabaci, Thrips palmi and Frankliniella    accidentalis.-   From the order of the Heteroptera, for example, Eurygaster spp.,    Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius    prolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decernlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsoneitus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

The compounds of the formula (I) according to the invention are active,in particular, against sucking insects.

At certain concentrations or application rates, the compounds accordingto the invention may, if appropriate, also be used as herbicides andmicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they may also be used as intermediates or precursors forthe synthesis of further active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, inclusive of the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodto mean all above-ground and underground parts and organs of plants,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

Solid carriers are:

-   for example ammonium salts and ground natural minerals such as    kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or    diatomaceous earth, and ground synthetic minerals, such as highly    disperse silica, alumina and silicates; suitable solid carriers for    granules are: for example crushed and fractionated natural rocks    such as calcite, marble, pumice, sepiolite and dolomite, and also    synthetic granules of inorganic and organic meals, and granules of    organic material such as sawdust, coconut shells, maize cobs and    tobacco stalks; suitable emulsifiers and/or foam-formers are: for    example nonionic and anionic emulsifiers, such as polyoxyethylene    fatty acid esters, polyoxyethylene fatty alcohol ethers, for example    alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates,    arylsulphonates and also protein hydrolysates; suitable dispersants    are: for example ligno-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphoric acid esters, carbamates,carboxylates, chlorinated hydrocarbons, phenylureas and substancesproduced by microorganisms, inter alia.

Particularly favourable examples of co-components in mixtures are thefollowing compounds:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, capsimycin, captafol, captan, carbendazim,    carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,    chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,    cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,-   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,    fentin hydroxide, ferbam, ferinmzone, fluazinam, flumetover,    fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulphamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazole-cis, furmecyclox,-   guazatine,-   hexachlorobenzene, hexaconazole, hymexazole,-   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,    iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),    iprodione, irumamycin, isoprothiolane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl, metconazole, methasulphocarb, methfuroxam, metirarn,    metomeclam, metsulphovax, mildiomycin, myclobutanil, myclozolin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,    ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,    oxyfenthiin,-   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,    pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,    procymidone, propamocarb, propanosine-sodium, propiconazole,    propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,    pyroxyfur,-   quinconazole, quintozene (PCNB),-   sulphur and sulphur preparations,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,    triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,    triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G,-   OK-8705,-   OK-8801,-   α-(1,    1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   1-isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,-   2,6-dichloro-5-(methylthio)₄-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecaroxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,    1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,-   ethyl [(4-chlorophenyl)-azo)-cyanoacetate,-   potassium hydrogen carbonate,-   methanetetrathiol sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)₄-methyl-3-nitro-benzenesulphonamide,-   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy)-3-pyridinyl-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino)-ethyl)-benzamide,-   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine sodium salt,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran-3′-one.    Bactericides:-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbasnate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.    Insecticides/Acaricides/Nematicides:-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin,    AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin,-   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus    thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella,    bendiocarb, benfiracarb, bensultap, benzoximate, betacyfluthrin,    bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC,    bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,    butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan,    cartap, chloetho-carb, chlorethoxyfos, chlorfenapyr,    chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos,    chlorpyrifos M, chlovaporthrin, cis-resmethrin, cispermethrin,    clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene,    cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,    cyromazine,-   deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,    diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos,    diofenolan, disulphoton, docusat-sodium, dofenapyn,-   eflusilanate, emrnamectin, empenthrin, endosulphan, Entomopfthora    spp., eprinomectin., esfenvalerate, ethiofencarb, ethion,    ethoprophos, etofenprox, etoxazole, etrimfos,-   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,    fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,    fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam,    fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,    flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan,    fosthiazate, fubfenprox, furathiocarb,-   granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, metharhizium    anisopliae, metharhizium flavoviride, methidathion, methiocarb,    methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,    milbemectin, monocrotophos, naled, nitenpyram, nithiazine,    novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,    propoxur, prothiofos, prothoate, pymetrozine, pyraclofos,    pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,    pyri-proxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, selamectin, silafluofen, spinosad, sulphotep,    sulprofos,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron, teflu-thrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, thetacypermethrin, thiamethoxam, thiapronil,    thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,    thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,    triazophos, triazurone, trichlophenidine, trichlorfon, triflumuron,    trimethacarb, vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302,-   zeta-cyperrnethrin, zolaprofos,-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)₄-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetlyoxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate,-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,-   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,-   ethyl    [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compounds according to the invention can furthermore bepresent when used as insecticides in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase, the action of the active compounds, without it beingnecessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahriia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonaptcrida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalommna spp., Rhipicephalus spp., Dermanyssusspp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroaspp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

They have, for example, good activity against Aphis spp. and Myzus spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injection(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention also have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as beingpreferred—but without any limitation:

-   Beetles, such as-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,    Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus    africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,    Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.,    Tryptodendron spec., Apate monachus, Bostrychus capucins,    Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus minutus.-   Hymenopterons, such as-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus    augur.-   Termites, such as-   Kalotermes flavicollis, Cryptoterines brevis, Heterotermes indicola,    Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes    lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and    Coptotermes formosanus.-   Bristletails, such as Lepisma saccharina.

Industrial materials in the present context are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentaccording to the invention or mixtures comprising this are to beunderstood as meaning, for example:

-   building timber, wooden beams, railway sleepers, bridge components,    boat jetties, wooden vehicles, boxes, pallets, containers, telegraph    poles, wood panelling, wooden windows and doors, plywood, chipboard,    joinery or wooden products which are used quite generally in    house-building or in building joinery.

The active compounds can be used as such, in the form of concentrates orin generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyes and pigments, and also other processing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compound,based on the material to be protected.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., turpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, provided that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-coumaroneresin, silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxideand triflumuron,

and also fungicides, such as epoxyconazole, hexaconazole, azaconazole,propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl-butyl carbamate,N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with salt wateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using compounds according to the invention, alone or in combination withother active compounds, allows the use of heavy metals such as, forexample, in bis-(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combination with the antifoulingcompositions according to the invention are:

-   algicides such as-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;-   fungicides such as-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as azaconazole, cyproconazole,    epoxyconazole, hexaconazole, metconazole, propiconazole and    tebuconazole;-   molluscicides such as-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb; or conventional antifouling active compounds such as-   4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulphone, 2-(N,N-di-methylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetra-methylthiuram disulphide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind 1985, 37, 730-732 and Williams, Antifouling MarineCoatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise; in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the theological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaces such as, for example, dwellings, factory halls, offices, vehiclecabins and the like. They can be employed in domestic insecticideproducts for controlling these pests alone or in combination with otheractive compounds and auxiliaries. They are active against sensitive andresistant species and against all developmental stages. These pestsinclude:

-   From the order of the Scorpionidea, for example, Buthus occitanus.-   From the order of the Acarina, for example, Argas persicus, Argas    reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus    domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula    alfreddugesi, Neutrombicula autumnalis, Dermatophagoides    pteronissimus, Dermatophagoides forinae.-   From the order of the Araneae, for example, Aviculariidae,    Araneidae.-   From the order of the Opiliones, for example, Pseudoscorpiones    chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.-   From the order of the Isopoda, for example, Oniscus asellus,    Porceliho scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus,    Polydesmus spp.-   From the order of the Chilopoda, for example, Geophilus spp.-   From the order of the Zygentoma, for example, Ctenolepisma spp.,    Lepisma saccharina, Lepismodes inquilinus.-   From the order of the Blattaria, for example, Blatta orientalies,    Blattella germanica, Blattella asahinai, Leucophaea maderae,    Panchlora spp., Parcoblatta spp., Periplaneta australasiae,    Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa,    Supella longipalpa.-   From the order of the Saltatoria, for example, Acheta domesticus.-   From the order of the Dermaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Kalotermes spp.,    Reticulitermes spp.-   From the order of the Psocoptera, for example, Lepinatus spp.,    Liposcelis spp.-   From the order of the Coleptera, for example, Anthrenus spp.,    Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp.,    Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus    oryzae, Sitophilus zeamais, Stegobium paniceum.-   From the order of the Diptera, for example, Aedes aegypti, Aedes    albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora    erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex    pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca    domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,    Stomoxys calcitrans, Tipula paludosa.-   From the order of the Lepidoptera, for example, Achroia grisella,    Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea    pellionella, Tineola bisselliella.-   From the order of the Siphonaptera, for example, Ctenocephalides    canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans,    Xenopsylla cheopis.-   From the order of the Hymenoptera, for example, Camponotus    herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,    Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.-   From the order of the Anoplura, for example, Pediculus humanus    capitis, Pediculus humanus corporis, Phthirus pubis.-   From the order of the Heteroptera, for example, Cimex hemipterus,    Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

They are used in the household insecticides sector alone or incombination with other suitable active compounds such as phosphoricesters, carbamates, pyrethroids, growth regulators or active compoundsfrom other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations;

PREPARATION EXAMPLES Example I-1

1-[6-Chloro-3-pyridylmethyl]-5-cyanoimino-7-methyl-4.5-dihydro[1,3]diazolano-[1,2-c][1,3]thiazoline

In a 100 ml two-necked flask, 10.0 mmol ofN-(6-chloro-3-pyridylmethyl)ethane-1,2-diamine (XI-1) are initiallycharged with 25 ml of abs. ethanol, and 1.89 g (11.0 mmol) of ethyl2-chloropropanealuminium chloride (XII) in 20 ml of abs. ethanol areadded dropwise at room temperature. After the addition has ended, themixture is stirred at room temperature for one hour. 1.70 g (10.0 mmol)of potassium N-cyanoiminomethylsulphanylmethanethiolate (XIV) are thenadded a little at a time with vigorous stirring, and the mixture isstirred at room temperature for one hour and under reflux for 90minutes. The hot reaction mixture is filtered directly into 60 ml ofwater. The filtrate is kept in a fridge overnight, giving the productsas crystals or as an oil. In both cases, the precipitate isrecrystallized from ethanol.

m.p.: 130° C.

yield: 0.82 g (27% of theory)

¹H-NMR₃₀₀ (DMSO-d₆/TMS)

δ/ppm=2.04 (s, 3H, H-14), 3.71 (m, 2H, H-9), 3.87 (m, 2H, H-10), 4.49(s, 2H, H-7), 7.56 (d, 1H, H-5, J=8.2 Hz), 7.87 (dd, 1H, H-4, J=8.2 Hz,J=2.5 Hz), 8.43 (d, 1H, H-2, J=2.5 Hz).

Example I-2

1-[6-Chloro-3-pyridylmethyl]-6-cyanoimino-8-methyl-1,2,3,4,5,8a,5.6-octahydro-[1,3]thiazolino[3.4-α]pyrimidine

is prepared analogously to Example I-1 usingN-(6-chloro-3-pyridylmethyl)propane-1,2-diamine (XI-2).

m.p.: 153° C.

yield: 1.09 g (34% of theory)

¹H-NMR₃₀₀(DMSO-d₆/TMS)

δ/ppm=1.92 (qui, 2H, H-10, ³J=5.9 Hz), 2.06 (s, 3H, H-15), 3.05 (t, 2H,H-9,³J=105.6 Hz), 3.77 (t, 2H, H-11, ³J=6.3 Hz), 4.40 (s, 2H, H-7), 7.55(d, 1H, H-5, J=8.2 Hz), 7.88 (dd, 1H, H-4, J=8.2 Hz, J=2.5 Hz), 8.41 (d,1H, H-2, J=2.5 Hz).

Example (XI-1)

At room temperature, 2.6 ml of abs. triethylamine are added to 0.06 molof ethane-1,2-diamine (3.61 g) and 100 ml of abs. acetonitrile. Over aperiod of two hours, 3.24 g (0.02 mol) of6-chloro-3-chloromethylpyridine (CCMP) in 100 ml of abs. acetonitrileare very slowly added dropwise, and the mixture is stirred for 20 hours.The reaction mixture is then filtered, the solvent is removed underreduced pressure using a rotary evaporator and the residue is subjectedto fractional distillation under high vacuum.

b.p.: 120° C./0.05 mbar

yield: 2.45 g (65% of theory)

¹H-NMR₃₀₀ (CDCl₃ S)

δ/ppm=1.41 (br, 3H, H-8 and H-11), 2.68 (m, 2H, H-10), 2.83 (m, 2H,H-9), 3.80 (s, 2H, H-7), 7.29 (d, 1H, H-5, J=8.1 Hz), 7.68 (dd, 1H, H-4,J=8.1 Hz, J=2.5 Hz), 8.34 (d, 1H, H-2, J=2.5 Hz).

Example (XI-2)

is prepared analogously to Example (IX-1) using propane-1,2-diamine(4.45 g).

b.p.: 125° C./0.05 mbar

yield: 2.48 g (62% of theory)

¹H-NMR₃₀₀(CDCl₃/TMS)

δ/ppm=1.38 (br, 3H, H-8 and H-12), 1.65 (qui, 2H, H-10, ³J=6.8 Hz), 2.69(t, 2H, H-11, ³J=6.8 Hz), 2.78 (t, 2H, H-9, ³J=6.8 Hz), 3.79 (s, 2H,H-7), 7.29 (d, 1H, H-5, J=8.1 Hz), 7.68 (dd, 1H, H-4, J=8.1 Hz, J=2.4Hz), 8.34 (d, 1H, H-2, J=2.4 Hz).

Example (XIV)

Potassium N-cyanoiminomethylsulphanylmethanethiolate

a) Preparation of the dipotassium salt of cyanoimidodithiocarbonic acid

Under an atmosphere of nitrogen, in a 500 ml four-necked flask fittedwith overhead stirrer, dropping funnel, thermometer and refluxcondenser, 21.0 g (0.50 mol) of cyanamide in 40 ml of ethanol are cooledto 0° C. At this temperature, 41.9 g (0.55 mol) of carbon disulphide andthen 56.1 g (1.00 mol) of potassium hydroxide in 180 ml of ethanol aresuccessively added dropwise such that the internal temperature does notexceed 5° C. (about 4 hours). After the addition has ended, the coolingbath is removed and the mixture is stirred at room temperatureovernight. The resulting solid is filtered off (a very fine precipitaterapidly blocks the pores of the frits), washed with ethanol and driedunder reduced pressure. The resulting salt is hygroscopic and, duringfiltration, should only be in contact with the atmosphere/atmospherichumidity for a short time. For the next step, the salt is used as crudeproduct. The yield is 75-80% of theory.

b) Potassium N-cyanoiminomethylsulphanylmethanethiolate

77.7 g (0.40 mol) of the crude product are dissolved in a mixture of 270ml of acetone and 300 ml of water and cooled to 0° C. At thistemperature, with vigorous stirring, 56.8 g (0.40 mol) of methyliodidein 150 ml of acetone are slowly added dropwise over a period of threehours. After the addition has ended, the reaction mixture is stirred at0° C. for one hour and then at room temperature for another three hours.On a rotary evaporator, all solvents are removed to dryness. The residueis taken up in 250 ml of abs. acetone and, using a rotary evaporator,concentrated to half of its original volume. For crystallization of theresulting potassium iodide, the reaction mixture is kept in a fridgeovernight. The resulting solid is filtered off and the filtrate isconcentrated further, almost to dryness. In the cold, the desiredproduct precipitates out. The last step can now be repeated to completeremove the potassium iodide. The yield is 75-80% of theory. Theanalytical data are consistent with the literature.

Example (XII-1)

Ethyl 2-chloropropaneiminium chloride

(cf. S. Shibata et al., Bull. Chem. Soc. Jpn. 55(11), 3546-3551 (1982))

In a flask which had been weighed and flushed with nitrogen, 35.00 g ofabs. diethyl ether, 2.30 g (50.0 mmol) of abs. ethanol and 4.48 g (50.0mmol) of 2-chloropropionitrile are brought to 0-5° C. With moderatestirring, 1.80 g (50.0 mmol) of hydrogen chloride gas, dried with conc.sulphuric acid, are then introduced slowly over 45-60 minutes. Theamount of hydrogen chloride introduced is determined by weighing theflask. Here, it is important to exclude moisture at all times. Withpermanent stirring, the reaction mixture is allowed to warm to roomtemperature over a period of 20 hours, resulting in the crystallizationof the product as a white powder. To bring the crystallization tocompletion, the reaction mixture is stored in the cold for another dayand then filtered, and the crude product, which is used without furtherwork-up, is dried at room temperature under high vacuum. Since theproduct is decomposed by small amounts of water, no analytic studieswere undertaken. The yield is 50-60% of theory.

Example (XV-1)

1.86 g (10.0 mmol) of N-(6-chloro-3-pyridylmethyl)ethane-1,2-diamine(XI-1) are dissolved in 25 ml of abs. ethanol and, at room temperature,a solution of 1.89 g (11.0 mmol) of ethyl 2-chloropropaneiminiumchloride (XII-1) in 20 ml of abs. ethanol is added dropwise. After theaddition has ended, the mixture is stirred at room temperature for onehour. To flush out the ammonia which has formed, a moderate stream ofnitrogen is, with vigorous stirring, passed through the reaction mixturefor four hours, the mixture is filtered and the solvent is removed underreduced pressure using a rotary evaporator. The oily residue is taken upin 25 ml of ethanol, 4.0 ml of 10% strength aqueous sodium hydroxidesolution are added on an ice bath and the mixture is stirred at roomtemperature for one hour. To isolate the product, the mixture isfiltered, the solvent is removed and the oily residue is chromatographedon silica gel using ethyl acetate/methanol 2/1 (R_(f) 0.2).

Yield: 1.69 g (71% of theory)

¹H-NMR₃₀₀(DMSO-d₆/TMS)

δ/ppm=1.22 (d, 3H, H-14, ³J=6.9 Hz), 2.83 (ddd, 1H, H-9, J=12.8 Hz,³J=9.8 Hz, ³J=4.3 Hz), 2.99 (ddd, 1H, H-9, ²J=12.8 Hz, ³J=4.7, Hz,³J=3.3 Hz), 3.15 (dt, 1H, H-10,²J=11.4 Hz, ³J=4.0 Hz), 3.31 (ddd, 1H,H-10, ²J=11.4 Hz, ³J=9.8 Hz, ³J=4.7 Hz), 4.51 (m, 2H, H-7), 7.50 (d, 1H,H-5, J=8.2 Hz), 7.73 (dd, 1H, H-4, J=8.2 Hz, J=2.5 Hz), 8.32 (d, 1H,H-2, J=2.5 Hz).

Example (XVI-1)

On an ice bath, a solution of 0.23 g (10.0 mmol) of sodium and 5 ml ofabs. ethanol is added dropwise to 0.76 g (10.0 mmol) of carbondisulphide and 10 ml of abs. ethanol, and, after the addition has ended,the mixture is stirred at room temperature for 30 minutes. In an icebath, this solution is added dropwise to the crude product (XV-1)dissolved in 25 ml of ethanol and the mixture is slowly warmed to roomtemperature and heated under reflux for 90 minutes. The hot mixture isthen filtered and the filtrate is concentrated. The product is obtainedin the form of pale yellow crystals. For purification, the product isrecrystallized from ethanol.

m.p.: 126° C.

yield: 1.36 g (54% of theory, based on XV-1)

¹H-NMR₃₀₀(DMSO-d₆/TMS)

δ/ppm=2.01 (s, 3H, H-14), 3.72 (m, 2H, H-9), 3.88 (m, 2H, H-10), 4.47(s, 2H, H-7), 7.55 (d, 1H, H-5, J=8.2 Hz), 7.88 (dd, 1H, H4, J=8.2 Hz,J=2.5 Hz), 8.44 (d, 1H, H-2, J=2.5 Hz).

Use Examples Example 1

Test with Cockroaches—Dip Treatment

Test animals: Third larval stages of Periplanela americana

Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in one ml of dimethyl sulphoxide.To prepare a suitable formulation, the solution of active compound isdiluted with water to the particular concentration desired.

20 ml of this preparation of active compound are pipetted into tubes (Ø1.5 cm, H 10 cm). 4 cockroach larvae are anaesthetized with CO₂ andtransferred into a tube (Ø 1.2 cm, H 9 cm) with 3 holes (bottom and 5 cmbelow the upper rim). The tube is closed with a stopper and kept at roomtemperature for 30 min until all cockroach larvae exhibit normalactivity again. The tube is dipped into the preparation of activecompound for 60 seconds, with all cockroach larvae being wettedcompletely. After the liquid has run off, the cockroach larvae aretransferred to filter discs in PP dishes (Ø 9.7 cm. H 8 cm).

After 2 and 24 hours and after 7 days, the activity of the preparationof active compound is determined. 100% means that all cockroach larvaehave been killed; 0% means that none of the cockroach larvae have beenkilled.

In this test, for example, the following compounds of the PreparationExamples show satisfactory activity:

% action (7 d) Compound 1000 ppm 300 ppm 100 ppm I-1 100 100 100

Example 2

Blowfly Larvae Test/Development-Inhibitory Action

Test animals: Lucilia cuprina larvae

Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in one ml of dimethyl sulphoxide.To prepare a suitable formulation, the solution of active compound isdiluted with water to the particular concentration desired.

About 20 Lucilia cuprina larvae are introduced into a test tube whichcontains about 1 cm³ of horsemeat and 0.5 ml of the preparation ofactive compound to be tested. The activity of the preparation of activecompound is determined after 48 hours as the mortality of the larvae in%.

The test tubes are then transferred into a beaker whose bottom iscovered with sand. After a further 12 days, the test tubes are removedand the pupae and flies are counted. The development-inhibitory actionis stated as inhibition of hatching in % (ratio of pupae to flies thathave hatched) after 1.5 times the development period of an untreatedcontrol.

In this test, for example, the following compounds of the PreparationExamples show satisfactory activity:

% action (mortality of larvae) Compound 1000 ppm 300 ppm 100 ppm I-1 100100 100

Example 3

Test with Cat Fleas/Oral Uptake

Test animals: Adults of Crenocephalides felis

Solvent: Dimethyl sulphoxide (DMSO)

To produce a suitable preparation, a suitable solution of activecompound is prepared from 20 mg of active compound and 1 ml of DMSO. 20μl of this formulation are added to 4 ml of citrated cattle blood andstirred.

20 unfed adult fleas (Ctenocephalides felis, strain “Georgi”) are placedinto a chamber (Ø 5 cm) whose top and bottom are closed with gauze. Ametal cylinder whose underside is covered with parafilm is placed ontothe chamber. The cylinder contains the 4 ml of blood/active compoundformulation which can be taken up by the fleas through the parafilmmembrane. Whereas the blood is warmed to 37° C., the temperature in thearea of the flea chambers is adjusted to 25° C. Controls are mixed withthe same volume of DMSO, without addition of a compound. Thedeterminations are carried out triplicate.

After 24 h, the mortality in % is determined.

Compounds which effect an at least 25% kill of the fleas within 24 h arejudged to be effective.

In this test, for example, the following compounds of the PreparationExamples are effective:

% action (mortality of larvae) Compound 100 ppm I-1 30

1. A compound of formula (I)

in which A represents optionally substituted aryl, hetaryl, orheterocyclyl, R¹ represents hydrogen or C₁-C₃-alkyl, R² representshydrogen, C₁-C₃-alkyl, or optionally substituted aryl or hetaryl, nrepresents 2, 3, or 4, Y represents N—CN or N—NO₂, Z represents S, SO,SO₂, or NR³, and R³ represents hydrogen or C₁-C₃-alkyl.
 2. A compound offormula (I) according to claim 1 in which A represents optionallyhalogen-, cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-,or C₁-C₄-haloalkoxy-substituted phenyl; represents pyrazolyl,1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,1,2,5-thiadiazolyl, pyridyl, pyrazinyl, or pyrimidinyl, each of which isoptionally substituted by fluorine, chlorine, bromine, cyano, nitro,C₁-C₂-alkyl that is optionally substituted by fluorine and/or chlorine,C₁-C₂-alkoxy that is optionally substituted by fluorine and/or chlorine,C₁-C₂-alkylthio that is optionally substituted by fluorine and/orchlorine, or C₁-C₂-alkylsulphonyl that is optionally substituted byfluorine and/or chlorine; or represents an optionally halogen- orC₁-C₃-alkyl-substituted saturated C₅-C₆-cycloalkyl radical in which onemethylene group is replaced by O or S, R¹ represents hydrogen, methyl,ethyl, n-propyl, or i-propyl, R² represents hydrogen, methyl, ethyl,n-propyl, or i-propyl; represents optionally halogen-, cyano-, nitro-,C₁-C₄-alkyl-, C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, orC₁-C₄-haloalkoxy-substituted phenyl; or represents pyrazolyl,1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,1,2,5-thiadiazolyl, pyridyl, pyrazinyl, or pyrimidinyl, each of which isoptionally substituted by fluorine, chlorine, bromine, cyano, nitro,C₁-C₂-alkyl that is optionally substituted by fluorine and/or chlorine,C₁-C₂-alkoxy that is optionally substituted by fluorine and/or chlorine,C₁-C₂-alkylthio that is optionally substituted by fluorine and/orchlorine, or C₁-C₂-alkylsulphonyl that is optionally substituted byfluorine and/or chlorine, n represents 2, 3, or 4, Y represents N—CN orN—NO₂, Z represents S or NR³, and R³ represents hydrogen, methyl, ethyl,n-propyl, or i-propyl.
 3. A compound of formula (I) according to claim 1in which A represents thiazolyl or pyridyl, each of which is optionallysubstituted by halogen or C₁-C₃-alkyl; or represents an optionallyhalogen- or C₁-C₃-alkyl-substituted tetrahydrofuryl radical, R¹represents hydrogen or methyl, R² represents hydrogen or methyl;represents phenyl that is optionally substituted by halogen, cyano, oroptionally fluorine- or chlorine-substituted methyl, ethyl, methoxy, orethoxy; or represents thiazolyl, pyridyl, or pyrazinyl, n represents 2or 3, Y represents NCN or NNO₂, Z represents S or NR³, and R³ representshydrogen or methyl.
 4. A compound of formula (I) according to claim 1 inwhich A represents one of the radicals

R¹ represents hydrogen or methyl, R² represents hydrogen or methyl, nrepresents 2 or 3, Y represents NCN or NNO₂, Z represents S or NR³, andR³ represents hydrogen or methyl.
 5. A process for preparing a compoundof formula (I)

in which A represents optionally substituted aryl, hetaryl, orheterocyclyl, R¹ represents hydrogen or C₁-C₃-alkyl, R² representshydrogen, C₁-C₃-alkyl, or optionally substituted aryl or hetaryl, nrepresents 2, 3, or 4, Y represents N—CN or N—NO₂, Z represents S, SO,SO₂, or NR³, and R³ represents hydrogen or C₁-C₃-alkyl, comprisingreacting a compound of formula (II)

in which A, R¹, R² n, and Z are as defined for formula (I), with acyanating agent or with a nitrating agent.
 6. A composition forcontrolling animal pests comprising one or more compounds of formula (I)according to claim
 1. 7. A method of controlling animal pests comprisingapplying an effective amount of a compound of formula (I) according toclaim 1 to an animal pest and/or to surroundings, environment, orstorage space thereof.
 8. A method of preparing a composition forcontrolling animal pests comprising mixing one or more compounds offormula (I) according to claim 1 with one or more diluents and/orsurfactants.